CN114425243A - Metal-organic framework material separation membrane and preparation method and application thereof - Google Patents
Metal-organic framework material separation membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN114425243A CN114425243A CN202011101303.4A CN202011101303A CN114425243A CN 114425243 A CN114425243 A CN 114425243A CN 202011101303 A CN202011101303 A CN 202011101303A CN 114425243 A CN114425243 A CN 114425243A
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- membrane
- metal
- solution
- separation membrane
- organic
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention provides a metal-organic framework material separation membrane and a preparation method of the metal-organic framework material separation membrane. The metal-organic framework material separation film comprises a base film and a metal-organic framework material functional layer, and the metal-organic framework material functional layer structure comprises polyhedral structures embedded into each other. The preparation method of the metal-organic framework material separation membrane comprises the steps of (1) preparing a solution containing a first organic solvent, an organic ligand, a metal compound and an auxiliary agent; (2) pretreating the base film, and introducing metal atoms in the metal compound in the step (1) on the surface of the base film; (3) and (3) mixing the base membrane pretreated in the step (2) with the solution in the step (1) to obtain a first mixture, and heating the first mixture to react to obtain the metal-organic framework material separation membrane. The organic gas separation membrane prepared by the invention has the properties of high separation coefficient, large flux, adhesion resistance, pollution resistance and the like in the application process.
Description
Technical Field
The invention relates to a metal-organic framework material separation membrane and a method for preparing the metal-organic framework material separation membrane, belonging to the technical field of organic gas separation membrane preparation.
Background
The gas membrane separation technology is a new technology for realizing the separation of organic matters and a gas phase main body by utilizing the high-efficiency selective permeability of a membrane material to the organic matters, and has the advantages of continuous process, no heat release, no secondary pollution, high recovery rate, low energy consumption, miniaturization and the like. The method is a mainstream technology for separating organic matters and treating Volatile Organic Compounds (VOCs) in developed countries at present, and has wide application in the fields of environmental protection, chemical engineering and biological pharmacy.
Most of the existing organic gas separation membranes are prepared from siloxane through a coating and crosslinking process, and Polydimethylsiloxane (PDMS) is mostly used. Block copolymer (PEBA) is also a commonly used functional layer material for organic gas separation membranes, which has both the properties of stiffness of Polyamide (PA) material and softness of Polyether (PE) material, which provides high permeability, preferentially to organic substances; the hard polyamide provides mechanical strength that will overcome membrane swelling due to excessive adsorption of organics and thus maintain a good permselectivity. At present, the flux of the PDMS membrane is larger, but the molecular structure is loose and is not easy to regulate, so that the separation coefficient is lower, and the selectivity to specific substances is difficult to improve. Although the PEBA membrane has the properties of two block molecules, the molecular composition is fixed, the structure is single, the PEBA membrane is usually compact, the separation coefficient is high, the overall flux is small, and the application is limited.
As originally recognized, the 'sieving mechanism' membrane is realized by strictly controlling the pore diameter of membrane pores, only allowing molecules smaller than the pore diameter of the membrane pores to pass through and retaining macromolecules so as to realize material separation, so that the membrane has high flux and high separation coefficient. However, the diameter of the gas molecules is mostly less than 1 nanometer, and the difference of the molecular diameters among the gas molecules is very small, so that the requirement on the membrane structure is extremely high to realize accurate screening. Currently, no gas separation membrane with a sieving mechanism can be commercialized.
Metal-organic framework Materials (MOFs) are a novel porous material developed in recent years, and have the advantages of adjustable pore size, high specific surface area, stable structure, easy functional modification and the like, so that the metal-organic framework materials become research hotspots of researchers at home and abroad. In the field of separation engineering, the metal-organic framework material is used as a novel adsorbent, and shows wide application prospects in the aspects of organic matter separation, ion removal in water and enrichment analysis. However, the method is used only as an adsorption process, and has problems such as a discontinuous process, a need for analysis, difficulty in regenerating the adsorbent, and a short life.
Patent CN 110052185 a discloses a modification method based on dopamine UiO-66 membrane. Vertically soaking a porous substrate in a precursor solution prepared by dissolving zirconium chloride and terephthalic acid in N, N-dimethylformamide by using a fixing frame, and carrying out heat treatment for 48-96h at constant temperature; carrying out ultrasonic treatment for 3-30 s to obtain a substrate with seed crystals; heat-treating the substrate with the deposited seed crystal at least twice according to the same manner until a continuous UiO-66 film is obtained; and (3) soaking the prepared membrane for the first time and soaking the prepared membrane for the second time to obtain the UiO-66 membrane grafted with polydopamine. The poly dopamine grafted UiO-66 membrane has almost no mutually embedded UiO-66 structure, so that the compactness of the membrane is poor, and the selectivity of the membrane on specific substances is difficult to improve.
Disclosure of Invention
The invention aims to solve the problems that the continuous and complete MOFs separation functional layer is difficult to obtain or the separation functional layer is not firmly combined with a base film and is easy to fall off and have defects in the prior art, the obtained separation film has small flux and low separation coefficient, the selectivity of specific substances is difficult to improve, the preparation process is discontinuous, and the like. Meanwhile, the coating is carried out outside the functional layer to form a protective layer, so that the defects possibly existing in the functional layer are filled, the functional layer is prevented from being polluted and damaged in the using process, the separation coefficient of the separation membrane is improved, and the service life of the separation membrane is prolonged. Meanwhile, the surface of the separation membrane has larger surface roughness and hydrophobicity, so that stronger anti-pollution capacity is obtained, and the contact, dissolution and permeation of material molecules and the surface of the membrane are facilitated, thereby improving the flux of the membrane.
According to a first aspect of the present invention, there is provided a MOFs separation film comprising a base film and a MOFs functional layer, said MOFs functional layer structure comprising a plurality of polyhedral structures embedded in each other.
The mutually embedded polyhedral structure in the invention means that a part structure of a polyhedron is inserted into other adjacent or similar polyhedral structures, or a polyhedron and one or more surrounding polyhedrons share part lattices.
According to some embodiments of the invention, the polyhedron is constructed from a plurality of crystal lattices, and two adjacent polyhedrons in the mutually embedded polyhedron structure share a crystal lattice.
According to some embodiments of the present invention, the distance between the centers of two adjacent polyhedrons in the mutually embedded polyhedral structure is less than the average value L of the lengths of the two adjacent polyhedrons, preferably less than 0.95L, and more preferably 0.2 to 0.9L.
In the present invention, the "average value L" means a half of the sum of the lengths of two polyhedrons, for example, the length of the polyhedron A is L1Length of polyhedron B is L2If L is equal to (L)1+L2)/2。
According to some embodiments of the invention, at least 20% of the polyhedrons of said MOFs functional layer are embedded in each other, preferably at least 30%, preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 80% of the polyhedrons are embedded in each other.
According to some embodiments of the invention, the polyhedron comprises a hexahedral structure and/or an octahedral structure.
According to some embodiments of the invention, the length of the polyhedron is 50-2000 nm.
According to some embodiments of the invention, the polyhedron is constructed from a plurality of crystal lattices, wherein the crystal lattices are composed of metal atoms and organic ligands.
According to a preferred embodiment of the invention, the metal atoms are chosen from zirconium atoms, niobium atoms, molybdenum atoms or cobalt atoms.
According to a preferred embodiment of the invention, the organic ligand is selected from terephthalic acid or nitroterephthalic acid.
According to some embodiments of the invention, the hexahedron has a length of 50 to 1000nm, wherein the hexahedron having a length of 400 to 600nm accounts for 50 to 80%.
According to some embodiments of the invention, the octahedron has a length of 200-2000nm, wherein the octahedron with a length of 800-1200nm is 60-80%.
The "length of the polyhedron" in the present invention refers to the maximum length between the vertices of the polyhedron.
According to some embodiments of the invention, each of the octahedrons or hexahedrons is constructed of a plurality of crystal lattices formed by groups of zirconium metal atoms and terephthalic acid.
According to some embodiments of the invention, said MOFs functional layers comprise one or more layers of mutually embedded polyhedral structure.
According to some embodiments of the invention, the pore size of the MOFsF functional layer is determined by the average size of the crystal lattice formed by the metal atoms and the organic.
According to some embodiments of the invention, the MOFs functional layers have an average pore size of 0.1 to 2.0nm, preferably 0.30 to 0.96 nm.
According to some embodiments of the invention, the thickness of the MOFs functional layer is 200-5000 nm.
According to some embodiments of the invention, the thickness of the MOFs functional layer is 1000-5000 nm.
According to some embodiments of the invention, the base film is selected from one or more of a polypropylene film, a polyethylene film, a polyvinyl chloride film, or a polytetrafluoroethylene film.
According to some embodiments of the invention, the pore size of the base membrane is 10 to 10000nm, preferably 50 to 5000nm, more preferably 200 to 1000 nm.
In some preferred embodiments of the present invention, the base film is a polypropylene film, a polyethylene film, a polyvinyl chloride film or a polytetrafluoroethylene film having a pore size of 50nm to 5000nm prepared by melt-spinning stretching or thermally induced phase separation.
According to some embodiments of the invention, said MOFs functional layers further comprise auxiliary functional layers.
According to some embodiments of the invention, the auxiliary functional layer is a portion that is repaired where it may be present that does not completely form an embedded octahedral or hexahedral structure.
According to some embodiments of the invention, the organic silicon layer is located on the organic silicon layer of the surface of the MOFs functional layer.
According to a second aspect of the present invention, there is provided a method for preparing a MOFs separation membrane, comprising the steps of:
(1) preparing a solution comprising a first organic solvent, an organic ligand, a first metal compound and an adjuvant selected from water or glacial acetic acid;
(2) pretreating the base film, and introducing metal atoms in the first metal compound in the step (1) into the surface of the base film;
(3) mixing the base membrane pretreated in the step (2) with the solution in the step (1) to obtain a first mixture, heating the first mixture to react, and preparing the MOFs separation membrane;
(4) optionally, cleaning the separation membrane to obtain the composite membrane.
According to some embodiments of the invention, in step (1), the molar ratio of the first organic solvent, the organic ligand and the first metal compound is (10-1000): (1-100): (1-100).
According to some embodiments of the invention, in step (1), the molar ratio of the first organic solvent, the organic ligand and the first metal compound is (100-1000): (1-10): (1-10).
According to some embodiments of the invention, in step (1), the molar ratio of the first organic solvent, organic ligand and first metal compound is (100-700):1:1, e.g. 100:1: 1. 200:1: 1. 250: 1: 1. 300, and (2) 300: 1: 1. 350: 1: 1. 420: 1: 1. 450: 1: 1. 550: 1: 1. 610: 1: 1. 650: 1:1 and any value in between.
According to some embodiments of the invention, in step (1), the molar ratio of the first organic solvent, the organic ligand, and the first metal compound is (400-600):1: 1.
According to some embodiments of the invention, in step (1), the molar ratio of the first organic solvent and the adjuvant water is 100 (0.005-0.05), such as 100:0.01, 100:0.03 or 100: 0.03.
According to some embodiments of the invention, in step (1), the molar ratio of the first organic solvent to the co-agent glacial acetic acid is 100 (20-60), such as 100:25, 100:30, 100:40 or 100: 50.
According to some embodiments of the invention, the first organic solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide and dimethylacetamide.
According to some embodiments of the invention, the organic ligand is selected from terephthalic acid and/or nitroterephthalic acid.
According to some embodiments of the invention, the first metal compound is selected from one or more of a zirconium compound, a niobium compound, a molybdenum compound and a cobalt compound, preferably zirconium tetrachloride.
According to some embodiments of the invention, the base film is selected from one or more of a polypropylene film, a polyethylene film, a polyvinyl chloride film, or a polytetrafluoroethylene film.
According to some embodiments of the invention, the pore size of the base membrane is 10 to 10000nm, preferably 50 to 5000nm, more preferably 200 to 1000 nm.
In some preferred embodiments of the present invention, the base film is a polypropylene film, a polyethylene film, a polyvinyl chloride film or a polytetrafluoroethylene film having a pore size of 50nm to 5000nm prepared by melt-spinning stretching or thermally induced phase separation.
According to some embodiments of the invention, the step (2) comprises the steps of:
(2A-1) preparing a solution comprising polyacrylic acid, polyvinyl alcohol, and a second metal compound,
(2A-2) coating the solution of the step (2A-1) on a base film.
According to some embodiments of the invention, the polyacrylic acid comprises polyacrylic acid and partially hydrolyzed polyacrylic acid.
According to some embodiments of the invention, the mass concentration of polyacrylic acid and polyvinyl alcohol in the solution of step (2A-1) is 500-2000 mg/L.
According to some embodiments of the invention, the molar ratio of the sum of the polyacrylic acid and the polyvinyl alcohol to the metal compound in the solution of step (2A-1) is 1 to 3: 1.
according to some embodiments of the present invention, the metal atom in the second metal compound is the same as the metal atom in the first metal compound in step (1), preferably the second metal compound is selected from one or more of a zirconium compound, a niobium compound, a molybdenum compound and a cobalt compound, preferably zirconium tetrachloride.
According to some embodiments of the invention, in step (2A-2)The ratio of the surface area of the base film to the volume of the solution obtained in the step (2A-1) is 0.1-10m2L, e.g. 0.8m2/L、1.2m2/L、1.5m2/L、1.7m2/L、2.3m2/L、2.5m2/L、2.7m2/L、3.0m2/L、3.5m2/L、4.0m2/L、4.5m2/L、5.0m2/L、5.5m2/L、6.0m2/L、6.5m2/L、7.0m2/L、7.5m2/L、8.0m2/L、8.5m2/L、9.0m2/L、9.5m2L and any value in between.
According to some embodiments of the invention, in step (2A-2), the ratio of the surface area of the base film to the volume of the solution obtained in step (2A-1) is 0.5 to 5m2/L。
In some preferred embodiments of the present invention, in the step (2A-2), the ratio of the surface area of the base film to the volume of the solution obtained in the step (2A-1) is 1 to 2m2/L。
In some preferred embodiments of the present invention, the step (2) comprises the following specific steps:
(a) mixing polyacrylic acid with a mass concentration of 1000mg/L, partially hydrolyzed polyacrylic acid, polyvinyl alcohol and zirconium tetrachloride according to a molar ratio of 2: 1, mixing and stirring for 1 hour to obtain a mixed solution;
(b) and (c) coating the solution generated in the step (a) on the surface of the base film, and drying to attach a certain amount of metal atoms on the surface of the base film.
According to some embodiments of the invention, the step (2) comprises the steps of:
(2B-1) preparing a solution comprising the metal complex represented by the formula I and a second organic solvent,
(2B-2) mixing the base film with the solution of the step (2B-1),
(2B-3) cleaning the mixed base film in the step (2B-2) by adopting a third solvent;
in the formula I, Q is selected from amido, carbonyl or alkylene of C1-C6; r1Selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy or halogen; m1The same metal atom as that in the first metal compound in the step (1), preferably M1Selected from zirconium atoms, niobium atoms, molybdenum atoms or cobalt atoms; m is 5 to 20; n is 1 to 10.
According to some embodiments of the invention, in formula I, Q is selected from amide groups, R1Selected from C3-C6 alkyl, m is 5-20; n is 1 to 10.
According to some embodiments of the invention, the metal complex of formula I is:
according to some embodiments of the invention, the metal complex of formula I is:
according to some embodiments of the present invention, the second organic solvent is selected from one or more of organic solvents capable of swelling the base film, preferably from aliphatic hydrocarbons of C5-C10, halogenated aliphatic hydrocarbons of C1-C10, aromatic hydrocarbons of C6-C20 and halogenated aromatic hydrocarbons of C6-C20, more preferably from one or more of n-pentane, n-hexane, trichloromethane, carbon tetrachloride, benzene and toluene.
According to some embodiments of the invention, the third solvent is selected from one or more of the solvents capable of deswelling the swollen base film, preferably from water.
According to some embodiments of the invention, the mass concentration of the metal complex represented by formula I in the solution of step (2B-1) is 500 to 2000 mg/L.
According to some embodiments of the invention, in step (2B-2), the ratio of the surface area of the base film to the volume of the solution obtained in step (2B-1) is 0.1 to 10m2L, e.g. 0.8m2/L、1.2m2/L、1.5m2/L、1.7m2/L、2.3m2/L、2.5m2/L、2.7m2/L、3.0m2/L、3.5m2/L、4.0m2/L、4.5m2/L、5.0m2/L、5.5m2/L、6.0m2/L、6.5m2/L、7.0m2/L、7.5m2/L、8.0m2/L、8.5m2/L、9.0m2/L、9.5m2L and any value in between.
According to some embodiments of the invention, in step (2B-2), the ratio of the surface area of the base film to the volume of the solution obtained in step (2B-1) is 0.5 to 5m2/L。
In some advantageous embodiments of the invention, in step (2B-2), the ratio of the surface area of the base film to the volume of the solution obtained in step (2B-1) is from 1 to 2m2/L。
In some preferred embodiments of the present invention, the step (2) comprises the following specific steps:
(a) dissolving an acrylic acid-N-tert-butyl acrylamide/zirconium complex in N-hexane, and dissolving the acrylic acid-N-tert-butyl acrylamide/zirconium complex in a solvent according to the mass concentration of 1000mg/L to prepare a uniform solution;
(b) immersing the basement membrane into the solution obtained in the step (a) for 1-24 hours, taking out, quickly transferring to deionized water for cleaning, taking out and drying to obtain the modified basement membrane, wherein a part of acrylic acid-N-tert-butyl acrylamide/zirconium complex is embedded into the surface layer of the embedded basement membrane structure, and a certain amount of stable zirconium atoms are introduced into the basement membrane.
According to some embodiments of the invention, the step (2) comprises the steps of:
(2C-1) preparing a solution containing the metal complex represented by the formula II,
(2C-2) mixing the base film with the solution of the step (2C-1) to obtain a mixture, and polymerizing the mixture under the microwave radiation condition;
in the formula II, X is selected from amido, carbonyl or alkylene of C1-C6; r2、R3And R4The same or different, each is independently selected from hydrogen, alkyl of C1-C6, alkoxy of C1-C6 or halogen; m2The same metal atom as that in the first metal compound in the step (1), preferably M2Selected from zirconium atoms, niobium atoms, molybdenum atoms or cobalt atoms.
According to some embodiments of the invention, in formula II, X is selected from amide; r2、R3And R4The same or different, each is independently selected from hydrogen, C1-C3 alkyl.
According to some embodiments of the invention, the metal complex represented by formula II is:
according to some embodiments of the invention, the metal complex represented by formula II is:
according to some embodiments of the invention, the solution of the metal complex in step (2C-1) is an aqueous solution of the metal complex.
According to some embodiments of the invention, the mass concentration of the metal complex represented by formula II in the solution of step (2C-1) is 500 to 20000 mg/L.
According to some embodiments of the invention, in step (2C-2), the ratio of the surface area of the base film to the volume of the solution obtained in step (2C-1) is 0.1 to 10m2L, e.g. 0.8m2/L、1.2m2/L、1.5m2/L、1.7m2/L、2.3m2/L、2.5m2/L、2.7m2/L、3.0m2/L、3.5m2/L、4.0m2/L、4.5m2/L、5.0m2/L、5.5m2/L、6.0m2/L、6.5m2/L、7.0m2/L、7.5m2/L、8.0m2/L、8.5m2/L、9.0m2/L、9.5m2L and any value in between.
According to some embodiments of the invention, in step (2C-2), the ratio of the surface area of the base film to the volume of the solution obtained in step (2C-1) is 0.5 to 5m2/L。
According to some preferred embodiments of the present invention, in the step (2C-2), the ratio of the surface area of the base film to the volume of the solution obtained in the step (2C-1) is 1 to 2m2/L。
According to some embodiments of the invention, in step (2C-2), the microwave radiation has a microwave intensity of 500-2000. mu.w/cm2。
According to some embodiments of the invention, in step (2C-2), the microwave radiation has a microwave frequency of 1000 to 200000 Hz.
In some preferred embodiments of the present invention, the step (2) comprises the following specific steps:
(a) dissolving an acrylic acid-N-bisallylenamine/zirconium complex in an aqueous solution to prepare a graft polymerization solution;
(b) soaking a base membrane in the graft polymerization solution prepared in the step (a);
(c) radiation graft polymerization is carried out under microwave radiation with certain intensity, methyl on the basement membrane is initiated to generate free radicals, and the free radicals and double bonds in an acrylic acid-N-diacrylenamine/zirconium complex in graft polymerization liquid are subjected to graft polymerization reaction, so that a modified basement membrane is obtained, and zirconium atoms are introduced to the surface.
In the invention, after the base film is pretreated, on one hand, metal atoms can be introduced on the base film to firmly combine the MOFs film and the base film, and on the other hand, the metal atoms introduced on the base film can provide metal nodes for the subsequent in-situ growth of the MOFs film, so that a mutually embedded structure can appear in the growth process of the MOFs film, and therefore, the generation of defects is avoided.
According to some embodiments of the present invention, in the step (3), the ratio of the surface area of the base film pretreated in the step (2) to the volume of the solution obtained in the step (1) is (0.01 to 100) m2/L, preferably (0.01-10) m2L; more preferably 0.5 to 2m2/L。
According to a preferred embodiment of the present invention, in the step (3), before adding the base film to the solution obtained in the step (1), the following treatment may be performed: washing the surface of a base membrane (or a manufactured membrane component) by sequentially adopting water and an organic solvent, and drying; the organic solvent is preferably ethanol, methanol or acetone; preferably, the base film (or the fabricated membrane module) is washed 2 times by water, washed 2 times by an organic solvent and dried.
According to some embodiments of the invention, the step (3) comprises:
and heating the first mixture to react the organic ligand with the metal oxide, and generating the MOFs material on the surface of the base membrane, thereby preparing the separation membrane.
According to a preferred embodiment of the present invention, in the step (3), the reaction temperature is 50 to 300 ℃, preferably, the reaction temperature is 100 to 200 ℃.
According to a preferred embodiment of the present invention, in the step (3), the reaction pressure is 0.01 to 0.5MPa (gauge pressure), preferably, the reaction pressure is 0.05 to 0.1MPa (gauge pressure).
According to a preferred embodiment of the present invention, in said step (3), the reaction time is 1-100h, such as 5h, 17h, 20h, 25h, 27h, 30h, 40h, 50h, 60h, 70h, 80h, 90h and any value in between.
According to a preferred embodiment of the present invention, in said step (3), the reaction time is comprised between 10 and 72h, preferably between 15 and 30 h.
According to a preferred embodiment of the present invention, the step (3) may be performed under an inert gas atmosphere, preferably an inert gas is nitrogen.
According to some embodiments of the invention, in the step (4), the separation membrane is taken out (or the polymerization solution in the membrane module is discharged); cleaning the surface of the polymerized membrane for many times by using an organic solvent and water, and removing the monomer and the solvent which are not completely reacted to obtain the MOFs organic gas separation membrane (or membrane component), wherein the organic solvent for cleaning the surface of the membrane comprises ethanol, methanol or acetone; preferably, the separation membrane is washed 2 times with water, 2 times with an organic solvent and dried.
According to some embodiments of the present invention, the inventive method of preparing a MOFs separation membrane further comprises the steps of:
(5) performing one or more repairing treatments on the MOFs separation membrane obtained in the step (3) or (4), wherein the repairing treatments preferably comprise:
(A) mixing the MOFs separation membrane with a solution containing a first organic solvent, an organic ligand, a first metal compound and an auxiliary agent to obtain a second mixture, wherein the auxiliary agent is selected from water or glacial acetic acid;
(B) heating the second mixture to react to prepare the MOFs separation membrane;
(C) optionally, cleaning the separation membrane to obtain the composite membrane.
According to some embodiments of the invention, step (a) comprises:
(A1) preparing a solution comprising a first organic solvent, an organic ligand, a first metal compound and an adjuvant selected from water or glacial acetic acid;
(A2) and (3) adding the MOFs separation membrane obtained in the step (2) or (3) into the solution obtained in the step (A1) to obtain a second mixture.
According to a preferred embodiment of the present invention, the molar ratio of the first organic solvent, the organic ligand and the first metal compound in step (a) is (10-1000): (1-100): (1-100); preferably (100-1000): (1-10): (1-10), more preferably (100-700):1:1, e.g. 100:1: 1. 200:1: 1. 250: 1: 1. 300, and (2) 300: 1: 1. 350: 1: 1. 400:1: 1. 420: 1: 1. 550: 1:1 or 600: 1: 1.1, 650: 1:1 and any value in between.
According to a preferred embodiment of the invention, in step (A), the molar ratio of the first organic solvent to the auxiliary water is 100 (0.005-0.05), for example 100:0.01, 100:0.03 or 100: 0.03.
According to a preferred embodiment of the invention, in step (A), the molar ratio of the first organic solvent to the auxiliary agent glacial acetic acid is 100 (20-60), for example 100:25, 100:30, 100:40 or 100: 50.
According to a preferred embodiment of the present invention, in the step (a2), the ratio of the surface area of the MOFs separation membrane to the volume of the solution of the step (a1) is (0.01-100) m2L; preferably (0.01-10) m2L; more preferably 1m2/L。
According to a preferred embodiment of the present invention, the step (B) comprises:
and heating the second mixture to enable the organic ligand to react with the first metal compound, and continuously generating the MOFs material on the surface of the MOFs organic gas separation membrane.
According to a preferred embodiment of the present invention, in the step (B), the reaction temperature is 50 to 300 ℃, the reaction pressure is 0.01 to 0.5MPa (gauge pressure), and the reaction time is 1 to 100 hours.
According to a preferred embodiment of the present invention, in the step (B), the reaction temperature is 100 to 200 ℃, the reaction pressure is 0.05 to 0.1MPa (gauge pressure), and the reaction time is 5 to 50 hours.
According to a preferred embodiment of the present invention, in said step (B), the reaction time is comprised between 10 and 20 h.
According to a preferred embodiment of the present invention, the step (B) may be performed under an inert gas atmosphere, preferably an inert gas is nitrogen.
According to some embodiments of the invention, in step (C), the separation membrane is withdrawn (or the polymerization solution in the membrane module is drained); cleaning the surface of the polymerized membrane for many times by using an organic solvent and water, and removing the monomer and the solvent which are not completely reacted to obtain the MOFs organic gas separation membrane (or membrane component), wherein the organic solvent for cleaning the surface of the membrane comprises ethanol, methanol or acetone; preferably, the separation membrane is washed 2 times with water, 2 times with an organic solvent and dried.
According to some embodiments of the present invention, the inventive method of preparing a MOFs separation membrane further comprises the steps of: and (3) coating the silane coating liquid on the surface of the MOFs separation membrane prepared in the step (3) or (4) or (B) or (C), and heating the MOFs separation membrane coated with the silane coating liquid to enable the silane coating liquid to generate a crosslinking reaction, so that the MOFs separation membrane comprising the organic silicon layer is prepared.
According to some embodiments of the present invention, the silane coating solution may be coated on the surface of the MOFs separation membrane prepared in step (4) or step (C) by dip coating, blade coating, or the like, so that the surface of the MOFs separation membrane is coated with the silane coating solution with a thickness of 1-100 micrometers, preferably 25 micrometers.
According to some embodiments of the invention, the temperature of the crosslinking reaction is 50 to 300 ℃, preferably 50 to 200 ℃, more preferably 150 ℃; the time is 0.1 to 20 hours, preferably 0.1 to 10 hours, more preferably 0.5 hour.
After cross-linking, a cross-linked silane protective layer is formed on the surface of the MOFs organic gas separation membrane.
According to some embodiments of the invention, the preparation of the silane coating liquid comprises the steps of:
s1, mixing and dissolving silane, a cross-linking agent and an organic solvent to obtain a mixed solution;
and S2, adding a catalyst into the mixed solution, and pre-crosslinking the mixed solution to obtain the silane coating solution.
According to some embodiments of the invention, the ratio of silane, crosslinker and organic solvent in step S1 (0.1-10): (0.1-10): (90-100), preferably (1-10): (1-10): (90-100), more preferably 9:1: 90.
According to the preferred embodiment of the invention, the silane can be a monomer of siloxane material, including one or more of dimethyl siloxane, cured silicone rubber and vulcanized silicone rubber which are mixed in any proportion; and/or, the cross-linking agent comprises ethyl orthosilicate or tetramethoxysilane; and/or the organic solvent comprises at least one of heptane, pentane, toluene, benzene, xylene and hexane, preferably n-hexane.
According to a preferred embodiment of the present invention, the catalyst may be an organotin-based catalyst such as dibutyltin dilaurate or a titanium complex-based catalyst such as tetrabutyl titanate; the catalyst is used in an amount of 0.01 to 1 wt%, preferably 0.01 to 0.1 wt%.
According to some embodiments of the present invention, the pre-crosslinking time in step S2 is 1 to 48 hours, preferably 10 to 30 hours, more preferably 24 hours; and/or the viscosity of the silane coating liquid is 100 to 50000mpa.s, preferably 100 to 5000mpa.s, more preferably 2000 mpa.s.
According to some embodiments of the present invention, the inventive method of preparing a MOFs separation membrane further comprises the steps of:
the prepared MOFs separation membrane is added into alkali liquor for treatment to regulate and control the aperture, chemical bonds of partial zirconium atoms and organic matters are broken in the regulation and control process, the permeability of a functional layer and the connectivity of internal crystal lattices are increased, and the required separation aperture and more appropriate flux are obtained.
According to some embodiments of the invention, the lye is preferably a sodium hydroxide solution having a pH of between 9 and 13; the addition is accompanied by stirring, which achieves a flow rate of 0.01 to 1m/s, preferably 0.1 m/s. The time is 10-120min, preferably 30-60 min.
According to a third aspect of the present invention, there is provided a MOFs separation membrane produced by the method for producing a MOFs separation membrane according to the second aspect.
According to a fourth aspect of the present invention, there is provided the use of the MOFs separation membrane of the first aspect or the MOFs separation membrane prepared by the method of the second aspect in organic matter separation.
According to some embodiments of the present invention, the MOFs separation membrane may be used for benzene, toluene, xylene, and other benzene-related organic substances.
According to some embodiments of the present invention, the MOFs separation membrane may be used for separation of methane, ethane, propane, butane, pentane, hexane, heptane, cyclohexane, isopentane, and other alkanes and unsaturated alkane gases such as ethylene, propylene, acetylene, butylene, styrene, and other volatile gases from nitrogen and air.
According to some embodiments of the invention, the separation may be one or more membrane separations.
According to some embodiments of the present invention, the MOFs separation membrane may be used in conjunction with cryogenic, dehydrogenation, and deoxygenation processes in helium purification separations.
According to some embodiments of the present invention, the MOFs separation membrane may be used in conjunction with cryogenic, rectification, PSA, separation of alkenes and alkanes.
According to some embodiments of the present invention, in the field of organic gas separation, the MOFs separation membrane may be developed as a complete process by condensation, adsorption, absorption, and other techniques.
Compared with the prior art, the MOFs separation membrane and the preparation method thereof provided by the invention have the following advantages:
(1) the preparation process is simple, the operation is easy, and the cost is low;
(2) the prepared MOFs functional layer has excellent chemical dissolution resistance, high temperature resistance and higher mechanical strength;
(3) polyhedrons in the MOFs functional layer are mutually embedded, spread on the surface of a base film, and are compact and continuous, the thickness is thin, and the pore size distribution is uniform, so that the film has high flux and high separation coefficient;
(4) the organic silicon protective layer has hydrophobicity and air permeability, and can avoid the damage of water vapor and particles to the MOFs functional layer;
(5) the high-performance organic gas separation membrane prepared by the method has the excellent performance, so the high-performance organic gas separation membrane is well applied to the fields of petrifaction, biology, medicine, energy, environmental protection and the like.
Drawings
FIG. 1 shows an electron microscope image of the surface of the MOFs organic gas separation membrane prepared in example 1;
FIG. 2 shows the surface electron microscope image of the MOFs organic gas separation membrane prepared in example 5;
FIG. 3 shows an electron microscope image of the surface of the MOFs organic gas separation membrane prepared in example 9;
FIG. 4 is an electron micrograph of the surface of a MOFs organic gas separation membrane prepared in example 13;
FIG. 5 is an electron micrograph of the surface of a MOFs organic gas separation membrane prepared in example 21;
FIG. 6 is a photograph of a polyvinylidene fluoride (PVDF) substrate of comparative example 1 after soaking in a precursor solution;
FIG. 7 is a photograph of a polyvinylidene fluoride (PVDF) substrate of comparative example 2 after soaking in a precursor solution;
FIG. 8 shows an electron microscope image of the surface of the MOFs organic gas separation membrane prepared in comparative example 3;
FIG. 9 shows an electron microscope image of the surface of the MOFs organic gas separation membrane prepared in comparative example 4;
FIG. 10 shows a schematic diagram of a membrane performance testing apparatus, wherein the reference numerals have the following meanings: 1. purging gas; 2. feeding gas; 3. a temperature sensor; 4. a humidity sensor; 5. a membrane module; 6. a pressure gauge; 7. gas chromatography; 8. soap film flow meter.
Detailed Description
The present invention will be further illustrated by the following examples, but is not limited to these examples.
The raw materials used in the examples are all commercially available, and the chemical products mentioned are all common chemical products in the prior art, unless otherwise specified.
(1) The structural formula of the N-t-butylacrylamide/zirconium acrylate complex in the examples is shown below:
the preparation method comprises the following steps: weighing 47g of acrylic acid, dissolving in 250g of deionized water, and adjusting the pH value to 7-9 by using a NaOH solution; 50g of deionized water is taken, 12g of Sodium Dodecyl Sulfate (SDS) and 8.9g of nonylphenol polyoxyethylene ether (NP) are added, and 3g of tert-butyl acrylamide monomer is dropwise added under the condition of continuously stirring uniformly to form a uniform and stable clear solution. Mixing the two solutions, putting the mixture into a heat-insulating polymerization kettle, introducing nitrogen to remove oxygen for about 10 minutes, and adding a redox initiator: ammonium persulfate-sodium bisulfite (two reagents are added into deionized water solution with the proportion of 1% according to 0.05g of solid pure product respectively), and the aeration and natural temperature rise reaction are stopped after the solution becomes viscous. After the reaction is finished after 6-8 hours, the product hydrogel is cut into pieces, dried at 50 ℃ and powdered to obtain the acrylic acid-tert-butyl acrylamide copolymer. The copolymer is dissolved in water according to a certain concentration, and zirconium acetate is added to obtain the polyacrylic acid complex zirconium-tert-butyl acrylamide copolymer.
(2) The structural formula of the N-bisacryleneamine/zirconium acrylate complex in the examples is shown below:
the preparation method comprises the following steps: weighing 120g of acrylic acid, dissolving in 80g of deionized water, and adjusting the pH value to 7-9 by using a NaOH solution; taking 20g of deionized water, and adding 6g of methylene bisacrylamide to form a uniform and stable clear solution; 95g of industrial # 5 white oil was taken, and a suitable amount of 7.65g of Span80 and 10g of Tween80 were added, and stirred to form a stable homogeneous solution. Mixing the first part of water phase and oil phase, emulsifying with emulsifying machine to form stable inverse emulsion, and cooling in polymerization kettle. Ammonium persulfate initiator solution and 0.05g of ammonium persulfate are added to prepare 1% deionized water solution. With uniform stirring and nitrogen blanket, a solution of sodium bisulfite (0.05g pure solid, made up as a 1% solution in deionized water) and a second portion of methylenebisacrylamide was added slowly dropwise. The reaction was slightly exothermic. Stirring was continued for 2 hours after the completion of the dropping. The emulsion was then removed and poured into isopropanol/acetone, resulting in a white precipitate. And centrifuging the precipitate, and washing with ethanol to obtain the copolymer of acrylic acid and methylene bisacrylamide. The copolymer was dissolved in water and zirconium acetate was added to obtain the above copolymer.
Test method
The nitrogen/organic vapor mixed gas was subjected to a membrane separation performance test using an analysis method described in literature (research on a hollow fiber composite membrane separation organic vapor/nitrogen system, shochun, tianjin university, 2005), and the test apparatus is shown in fig. 10.
The typical structure of a gas separation membrane is a very thin dense layer overlaid on a porous support. The true thickness of the dense layer is difficult to determine accurately, and therefore, the permeability coefficient and the effective thickness of the membrane are often used in combination, and their ratio, called the permeation rate, is calculated by the following formula:
Ji＝(P/l)i＝Q/(Δp·A) (1-1)
in the above formula JiIs the permeation rate of the gas i component in mol/(m)2s.Pa); p is the permeability coefficient of the gas i component and has the unit of mol.m/(m)2s.Pa); l is the effective thickness of the film in m; qiThe molar flow under the standard condition of the i component in the permeating gas is expressed in mol/s; Δ p is the osmotic pressure difference in Pa; a is the membrane area in m2。
Separation coefficient α is calculated by the following equation
αN2 organic gas＝JN2/JOrganic gas (1-2)
[ example 1 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water according to the molar ratio of 400:1:1:0.01, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Mixing polyacrylic acid with a mass concentration of 1000mg/L, partially hydrolyzed polyacrylic acid, polyvinyl alcohol and zirconium tetrachloride according to a molar ratio of 2: 1, mixing and stirring for 1 hour to obtain a solution after reaction;
(b) washing polypropylene hollow fiber basal membrane with the aperture of 500nm with water, washing with ethanol, and drying, wherein the ratio of the surface area of the basal membrane to the solution in (a) is 1m2L (i.e. 1L of the prepared solution of step (a)) of film coating with a surface of 1 square meter, coating the dried surface of the base film with the solution generated in step (a), and drying to attach a certain amount of zirconium atoms on the surface of the base film.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2The membrane with the surface of 1 square meter is put into 1L of MOFs preparation solution in the step (1A), the membrane is immersed into the MOFs preparation solution to prepare a first mixture, nitrogen is introduced for protection, and the in-situ growth reaction is carried out for 24 hours at the temperature of 120 ℃ to prepare the separation membrane。
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The surface electron microscope of the prepared film is shown in figure 1, and as can be seen from figure 1, the MOFs functional layer of the prepared film consists of octahedral crystals which are embedded with each other, the MOFs functional layer is spread on the surface of a base film, is dense and continuous, has high surface roughness, is completely covered by the base film, and has few defects of the functional layer.
The performance test data of the membrane are shown in Table 1, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 4.828 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.301X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 16.03.
[ example 2 ]
The difference from example 1 is only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) is 0.1m2Coating the dried base film with the solution prepared in step (a) at a rate of 0.1 square meter of film coating.
The performance test data of the membrane are shown in Table 1, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 2.01 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.18X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 11.17.
[ example 3 ]
The difference from example 1 is only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) is 5m2L (i.e., 5 square meters of film coating 1L of the prepared solution of step (a)), and coating the solution produced in step (a) on the surface of the dried base film.
The film performance test data are shown in Table 1, and the film performance testTest data show that the flux of the nitrogen under 0.1Mpa can reach 10.41 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 1.206X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 8.63.
[ example 4 ]
The difference from example 1 was only in (2) pretreatment of the base film in terms of the ratio of the surface area of the base film to the solution described in (a) being 10m2L (i.e., film coating with a surface of 10 square meters 1L of the preparation solution described in step (a)), the solution produced in step (a) is coated on the surface of the dried base film.
The performance test data of the membrane are shown in Table 1, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 17.733 multiplied by 10-6mol/(m2s.Pa) and a flux of 1.909X 10 of propylene gas-6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 9.29.
TABLE 1
[ example 5 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water according to the molar ratio of 400:1:1:0.01, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Dissolving an acrylic acid-N-tert-butyl acrylamide/zirconium complex in N-hexane, and dissolving the acrylic acid-N-tert-butyl acrylamide/zirconium complex in the N-hexane according to the mass concentration of 1000mg/L to prepare a uniform solution;
(b) washing polypropylene hollow fiber base membrane with aperture of 500nm with water, washing with ethanol, drying, and dryingThe ratio of the film surface area to the solution described in (a) is 1m2And L (namely placing the membrane with the surface of 1 square meter into 1L of the preparation solution in the step (a)), immersing the dried basement membrane into the preparation solution in the step (a) for 2 hours, taking out the basement membrane, quickly transferring the basement membrane into deionized water for cleaning, taking out the basement membrane after drying to obtain the modified basement membrane, embedding a part of acrylic acid-N-tert-butyl acrylamide/zirconium complex into the embedded structural surface layer of the basement membrane, and introducing a certain amount of stable zirconium atoms into the basement membrane.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at the temperature of 200 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The surface of the obtained film was subjected to electron microscopy as shown in FIG. 2.
The performance test data of the membrane are shown in Table 2, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.521 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.088X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 17.28.
[ example 6 ]
The difference from example 5 is only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) is 0.1m2L (i.e., a film having a surface of 0.1 square meter is put into 1L of the preparation solution of the step (a)), and the dried base film is immersed into the preparation solution of the step (a).
The performance test data of the membrane are shown in Table 2, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.01 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.12X 10- 6mol/(m2s.Pa), and the nitrogen/propylene separation coefficient was 8.42.
[ example 7 ]
The difference from example 5 is only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) is 5m2L (i.e., a film having a surface of 5 square meters is put into 1L of the preparation solution of the step (a)), and the dried base film is immersed into the preparation solution of the step (a).
The performance test data of the membrane are shown in Table 2, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 2.89 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.188X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 15.37.
[ example 8 ]
The difference from example 5 was only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 10m2L (i.e., a film having a surface of 10 square meters is put into 1L of the preparation solution of the step (a)), and the dried base film is immersed into the preparation solution of the step (a).
The performance test data of the membrane are shown in Table 2, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 3.50 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.215X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 16.28.
TABLE 2
[ example 9 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water according to the molar ratio of 100:1:1:0.001, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Dissolving an acrylic acid-N-bisallylenamine/zirconium complex into the solution, and dissolving the acrylic acid-N-bisallylenamine/zirconium complex into water according to the mass concentration of 1000mg/L to prepare a graft polymerization solution;
(b) washing polypropylene hollow fiber basal membrane with the aperture of 500nm with water, washing with ethanol, and drying, wherein the ratio of the surface area of the basal membrane to the solution in (a) is 1m2(ii)/L (i.e., a film having a surface of 1 square meter is put into 1L of the preparation solution of the step (a)), the dried base film is immersed into the preparation solution of the step (a) at 1000. mu.w/cm2Radiation graft polymerization is carried out for 2h under the microwave radiation with the intensity frequency of 1000-200000Hz, methyl on the polypropylene microporous membrane is initiated to generate free radicals to carry out graft polymerization with double bonds in the acrylic acid-N-diacrylenamine/zirconium complex in graft polymerization liquid, so as to obtain a modified basement membrane, and zirconium atoms are introduced to the surface.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at the temperature of 200 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The surface of the obtained film was subjected to electron microscopy as shown in FIG. 3.
The performance test data of the membrane are shown in Table 3, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.41 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.047X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 30.00.
[ example 10 ]
And embodiments thereof9 is different only in (2) pretreatment of the base film in that the ratio of the surface area of the base film to the solution described in (a) is 0.1m2L (i.e., a membrane with a surface of 0.1 square meter is placed in 1L of the preparation solution of the step (a)), and the dried base membrane is immersed in the preparation solution of the step (a) to be subjected to radiation graft polymerization.
The performance test data of the membrane are shown in Table 3, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 0.341 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.0114X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 29.91.
[ example 11 ]
The difference from example 9 is only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) is 5m2L (i.e., a membrane having a surface of 5 square meters is placed in 1L of the preparation solution of step (a)), and the dried base membrane is immersed in (a) the preparation solution to be subjected to radiation graft polymerization.
The performance test data of the membrane are shown in Table 3, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.884 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.074X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 25.46.
[ example 12 ]
The difference from example 9 was only in (2) pretreatment of the base film in terms of a ratio of the surface area of the base film to the solution described in (a) of 10m2L (i.e., a film having a surface of 10 square meters is put into 1L of the preparation solution of the step (a)), immersing the dried base film into the preparation solution of the step (a) to perform radiation graft polymerization.
The performance test data of the membrane are shown in Table 3, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 2.984 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.121X 10- 6mol/(m2s.Pa) nitrogen/propylene separation coefficient of24.66。
TABLE 3
[ example 13 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and glacial acetic acid according to the molar ratio of 400:1:1:150, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Mixing polyacrylic acid with a mass concentration of 1000mg/L, partially hydrolyzed polyacrylic acid, polyvinyl alcohol and zirconium tetrachloride according to a molar ratio of 2: 1, mixing and stirring for 1 hour to obtain a solution after reaction;
(b) washing a polyethylene hollow fiber basal membrane with the aperture of 500nm with water, washing with ethanol and drying, wherein the ratio of the surface area of the basal membrane to the solution in (a) is 1m2L (i.e. 1L of the prepared solution of step (a)) of film coating with a surface of 1 square meter, coating the dried surface of the base film with the solution generated in step (a), and drying to attach a certain amount of zirconium atoms on the surface of the base film.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at the temperature of 200 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The surface of the obtained film was subjected to electron microscopy as shown in FIG. 4.
The film performance test data are shown in Table 4, and the film performance test data show that the mixed gas of propylene and nitrogen is at 0.1MPaThe flux of nitrogen can reach 0.896 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.047X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 19.06.
[ example 14 ]
The difference from example 13 is only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 0.1m2Coating the dried base film with the solution prepared in step (a) at a rate of 0.1 square meter of film coating.
The performance test data of the membrane are shown in Table 4, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 0.288 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.0095X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 30.32.
[ example 15 ]
The difference from example 13 is only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 5m2L (i.e., 5 square meters of film coating 1L of the prepared solution of step (a)), and coating the solution produced in step (a) on the surface of the dried base film.
The performance test data of the membrane are shown in Table 4, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.208 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.1659X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 7.28.
[ example 16 ]
The difference from example 13 was only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 10m2L (i.e., film coating with a surface of 10 square meters 1L of the preparation solution described in step (a)), the solution produced in step (a) is coated on the surface of the dried base film.
The film performance test data are shown in Table 4, the number of performance tests for the filmIt is shown that the flux of the nitrogen under 0.1MPa can reach 1.48 multiplied by 10 for the mixed gas of the propylene and the nitrogen-6mol/(m2s.Pa) and the flux of propylene gas is only 0.2659X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 5.57.
TABLE 4
[ example 17 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and glacial acetic acid according to a molar ratio of 200:1:1:100, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Dissolving an acrylic acid-N-tert-butyl acrylamide/zirconium complex in N-hexane, and dissolving the acrylic acid-N-tert-butyl acrylamide/zirconium complex in the N-hexane according to the mass concentration of 1000mg/L to prepare a uniform solution;
(b) washing a polyethylene hollow fiber basal membrane with the aperture of 500nm by water, washing by ethanol and drying, and then, according to the ratio of the surface area of the basal membrane to the solution in (a) being 10m2And L (namely placing the membrane with the surface of 10 square meters into 1L of the preparation solution in the step (a)), immersing the dried basement membrane into the preparation solution in the step (a) for 10 hours, taking out the basement membrane, quickly transferring the basement membrane into deionized water for cleaning, taking out the basement membrane after drying to obtain the modified basement membrane, and embedding a part of acrylic acid-N-tert-butyl acrylamide/zirconium complex compound into the surface layer of the embedded basement membrane structure to introduce a certain amount of stable zirconium atoms into the basement membrane.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at the temperature of 200 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The performance test data of the membrane are shown in Table 5, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 2.468 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.115X 10- 6mol/(m2s.Pa), and the nitrogen/propylene separation coefficient was 21.46.
[ example 18 ]
The difference from example 17 was only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 0.1m2L (i.e., a film having a surface of 0.1 square meter is put into 1L of the preparation solution of the step (a)), and the dried base film is immersed into the preparation solution of the step (a).
The performance test data of the membrane are shown in Table 5, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 0.3008 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.0184X 10-6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 16.35.
[ example 19 ]
The difference from example 17 was only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 1m2L (i.e., a film having a surface of 1 square meter is put into 1L of the preparation solution of the step (a)), and the dried base film is immersed into the preparation solution of the step (a).
The performance test data of the membrane are shown in Table 5, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.241 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.038X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 32.66.
[ example 20 ]
Comparison with example 17The only thing is that in (2) pretreatment of the base film, the ratio of the surface area of the base film to the solution in (a) is 5m2L (i.e., a film having a surface of 5 square meters is put into 1L of the preparation solution of the step (a)), and the dried base film is immersed into the preparation solution of the step (a).
The performance test data of the membrane are shown in Table 5, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 2.198 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.087X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 25.26.
TABLE 5
[ example 21 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and glacial acetic acid according to the molar ratio of 1000:1:1:500, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Dissolving an acrylic acid-N-bisallylenamine/zirconium complex into the solution, and dissolving the acrylic acid-N-bisallylenamine/zirconium complex into pure water according to the mass concentration of 1000mg/L to prepare a graft polymerization solution;
(b) washing a polyethylene hollow fiber basal membrane with the aperture of 500nm with water, washing with ethanol and drying, wherein the ratio of the surface area of the basal membrane to the solution in (a) is 1m2(ii)/L (i.e., a film having a surface of 1 square meter is put into 1L of the preparation solution of the step (a)), the dried base film is immersed into the preparation solution of the step (a) at 1000. mu.w/cm2Radiation graft polymerization is carried out for 2h under the microwave radiation with the intensity frequency of 1000-200000Hz, methyl on the polypropylene microporous membrane is initiated to generate free radicals to carry out graft polymerization with double bonds in the acrylic acid-N-diacrylenamine/zirconium complex in graft polymerization liquid, so as to obtain a modified basement membrane, and zirconium atoms are introduced to the surface.
(3) According toThe ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at the temperature of 200 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The surface of the obtained film was subjected to electron microscopy as shown in FIG. 5.
The performance test data of the membrane are shown in Table 6, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 0.889 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.042X 10- 6mol/(m2s.Pa), and the nitrogen/propylene separation coefficient was 21.17.
[ example 22 ]
The difference from example 21 was only that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 0.1m2L (i.e., a membrane with a surface of 0.1 square meter is placed in 1L of the preparation solution of the step (a)), and the dried base membrane is immersed in the preparation solution of the step (a) to be subjected to radiation graft polymerization.
The performance test data of the membrane are shown in Table 6, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 0.152 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.0112X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 13.57.
[ example 23 ]
The only difference from example 21 was that (2) in pretreatment of the base film, the ratio of the surface area of the base film to the solution described in (a) was 5m2L (i.e., a film having a surface of 5 square meters is put into 1L of the preparation solution described in the step (a)), and the dried base film is immersedThe preparation solution is subjected to radiation graft polymerization.
The performance test data of the membrane are shown in Table 6, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.055 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.087X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 12.13.
[ example 24 ]
The difference from example 21 was only in (2) pretreatment of the base film in terms of the ratio of the surface area of the base film to the solution described in (a) being 10m2L (i.e., a membrane having a surface of 5 square meters is placed in 1L of the preparation solution of step (a)), and the dried base membrane is immersed in (a) the preparation solution to be subjected to radiation graft polymerization.
The performance test data of the membrane are shown in Table 6, and the performance test data of the membrane show that the flux of the mixed gas of propylene and nitrogen and the nitrogen under 0.1Mpa can reach 1.386 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.114X 10- 6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 12.16.
TABLE 6
[ examples 25 to 29 ]
(1) Solution required for preparing MOFs membrane
N-methylpyrrolidone, terephthalic acid, zirconium tetrachloride and pure water were mixed in a molar ratio of 50:1:1:0.0005, 100:1:1:0.001, 200:1:1:0.002, 500:1:1:0.005 and 1000:1:1:0.001, and sufficiently stirred to obtain a solution required for the preparation of MOFs membranes.
(2) Pretreatment of base film
(a) Mixing polyacrylic acid with a mass concentration of 1000mg/L, partially hydrolyzed polyacrylic acid, polyvinyl alcohol and zirconium tetrachloride according to a molar ratio of 2: 1, mixing and stirring for 1 hour to obtain a solution after reaction;
(b) polymerizing with a pore diameter of 500nmWashing the propylene hollow fiber base membrane with water, washing with ethanol, and drying, wherein the ratio of the surface area of the base membrane to the solution in (a) is 1m2L (i.e. 1L of the prepared solution of step (a)) of film coating with a surface of 1 square meter, coating the dried surface of the base film with the solution generated in step (a), and drying to attach a certain amount of zirconium atoms on the surface of the base film.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at 120 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The separation membranes prepared in examples 25 to 29 were subjected to the separation coefficient and membrane flux tests for n-hexane gas and nitrogen gas, and the performance test data of the membranes are shown in Table 7.
TABLE 7
As can be seen from the data in Table 7, the separation membrane prepared showed a tendency of increasing the nitrogen/n-hexane separation coefficient from 34 to 51, and a slight increase in flux from 1.5X 10 as the specific gravity of the monomer content in the formulation decreased (the concentration decreased)-6mol/(m2s.Pa) to nearly 3X 10-6mol/(m2s.Pa). The main reason is that the in-situ polymerization reaction is more orderly along with the reduction of the monomer concentration, the structure of the formed functional layer is more compact, the defects are fewer, and the crystallinity is higher, which is beneficial to the improvement of the separation coefficient. When the monomer concentration is higher, the reaction speed is high, the ligand concentration is high, and oligomers and agglomeration phenomena are easily formed, so that the crystal structure is loose but the oligomers are not easy to formClogging of the channels results in a reduction in both separation factor and flux. While the formula 29, i.e. the mixture ratio is 1000:1:1:0.01, the separation coefficient is reduced to less than 10, and the flux exceeds 10 x 10-6mol/(m2s.Pa). This indicates that when the monomer concentration is too low, the MOFs functional layer has more defects, the flux is greatly increased, and the separation performance of the membrane cannot be maintained for a long time.
[ examples 30 to 37 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water according to a molar ratio of 500:1:1:0.005, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Mixing polyacrylic acid with a mass concentration of 1000mg/L, partially hydrolyzed polyacrylic acid, polyvinyl alcohol and zirconium tetrachloride according to a molar ratio of 2: 1, mixing and stirring for 1 hour to obtain a solution after reaction;
(b) washing polypropylene hollow fiber basal membrane with the aperture of 500nm with water, washing with ethanol, and drying, wherein the ratio of the surface area of the basal membrane to the solution in (a) is 1m2L (i.e. 1L of the prepared solution of step (a)) of film coating with a surface of 1 square meter, coating the dried surface of the base film with the solution generated in step (a), and drying to attach a certain amount of zirconium atoms on the surface of the base film.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 6h, 12h, 18h, 24h, 30h, 36h, 42h and 48h at the temperature of 120 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) And (5) cleaning the separation membrane in the step (4) to obtain the MOFs organic gas separation membrane.
The separation membranes prepared in examples 30 to 37 were subjected to the n-hexane gas and nitrogen gas separation coefficient and membrane flux tests, and the performance test data of the membranes are shown in Table 8.
TABLE 8
As can be seen from the data in Table 8, when the reaction time was increased from 12h to 24h, the separation coefficient of the MOFs separation membrane was rapidly increased from 30 to 50, and it was found that the formation of the MOFs functional layer provided the membrane with the separation effect on nitrogen/n-hexane. While the gas permeation flux can still be maintained at 3.0 × 10-6mol/(m2s.Pa) or higher. The functional layer is composed of UIO-66 with uniform pore size distribution and extremely high porosity, the lattice pore size of the functional layer is 0.6 nanometers and is slightly smaller than the size of n-hexane molecules, so that the functional layer blocks the n-hexane molecules from passing through, and the nitrogen molecules with the diameter of 3.4-3.6 nanometers can pass through the MOFs membrane, so that the flux is very high.
The separation coefficient remained stable at 52 with further increase of reaction time, while the flux gradually decreased, reaction time 48h, and flux decreased to less than 1.5X 10-6mol/(m2s.Pa) or less. This indicates that the reaction can form a continuous dense separation layer at 24 h. The further increase of the reaction time only increases the thickness of the functional layer, even leads to that a part of oligomers, monomers and solvents are wrapped in the functional layer to block the pores of the membrane, and leads to the reduction of the permeation flux. Therefore, the optimal reaction time is 18-24 h. Under the condition that the separation coefficient reaches 50, the nitrogen permeation flux exceeds 3.1 multiplied by 10-6mol/(m2s.Pa) is 10-15 times of the flux of the prior silicon rubber organic gas separation membrane and more than 30 times of the flux of the imported polyimide hydrogen separation membrane.
[ example 38 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water according to the molar ratio of 400:1:1:0.01, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Mixing polyacrylic acid with a mass concentration of 1000mg/L, partially hydrolyzed polyacrylic acid, polyvinyl alcohol and zirconium tetrachloride according to a molar ratio of 2: 1, mixing and stirring for 1 hour to obtain a solution after reaction;
(b) washing polypropylene hollow fiber basal membrane with the aperture of 500nm with water, washing with ethanol, and drying, wherein the ratio of the surface area of the basal membrane to the solution in (a) is 1m2L (i.e. 1L of the prepared solution of step (a)) of film coating with a surface of 1 square meter, coating the dried surface of the base film with the solution generated in step (a), and drying to attach a certain amount of zirconium atoms on the surface of the base film.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at 120 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) Mixing the MOFs organic gas separation membrane prepared in the step (4) with a solution containing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water to prepare a second mixture, wherein the molar ratio of the N-methyl pyrrolidone, the terephthalic acid, the zirconium tetrachloride and the pure water is 400:1:1:0.01, and the ratio of the membrane surface area to the solution containing the N-methyl pyrrolidone, the terephthalic acid, the zirconium tetrachloride and the pure water is 0.5m2/L。
(6) And (4) heating the second mixture obtained in the step (5) at 120 ℃ for reaction for 12 hours to obtain the separation membrane.
(7) And (5) cleaning the separation membrane in the step (6) to obtain the MOFs organic gas separation membrane.
The performance test data of the film shows that the nitrogen gas is under 0.1MpaThe flux of the magnetic flux can reach 3.120 multiplied by 10-6mol/(m2s.Pa) and the flux of propylene gas is only 0.089X 10-6mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 35.05.
[ example 39 ]
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water according to the molar ratio of 400:1:1:0.01, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Pretreatment of base film
(a) Mixing polyacrylic acid with a mass concentration of 1000mg/L, partially hydrolyzed polyacrylic acid, polyvinyl alcohol and zirconium tetrachloride according to a molar ratio of 2: 1, mixing and stirring for 1 hour to obtain a solution after reaction;
(b) washing polypropylene hollow fiber basal membrane with the aperture of 500nm with water, washing with ethanol, and drying, wherein the ratio of the surface area of the basal membrane to the solution in (a) is 1m2L (i.e. 1L of the prepared solution of step (a)) of film coating with a surface of 1 square meter, coating the dried surface of the base film with the solution generated in step (a), and drying to attach a certain amount of zirconium atoms on the surface of the base film.
(3) The ratio of the surface area of the pretreated base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at 120 ℃ to prepare the separation membrane.
(4) And (4) taking out the separation membrane prepared in the step (3), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(5) Mixing the MOFs organic gas separation membrane prepared in the step (4) with a solution containing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water to prepare a second mixture, wherein the molar ratio of the N-methyl pyrrolidone to the terephthalic acid to the zirconium tetrachloride to the pure water is 400:1:1:0.01, the surface area of the membrane is equal to that of the solution containing the N-methyl pyrrolidone, the terephthalic acid to the zirconium tetrachloride to the pure waterThe ratio of the liquid is 0.5m2/L。
(6) And (4) heating the second mixture obtained in the step (5) at 120 ℃ for reaction for 12 hours to obtain the separation membrane.
(7) Siloxane coating:
mixing room-temperature hydroxyl silane, ethyl orthosilicate and n-hexane according to the proportion of 1:0.2:8.8, stirring at a high speed for 24 hours, dissolving, adding 0.01% of dibutyltin dilaurate, and pre-crosslinking for 5 hours to obtain a silane coating solution with the viscosity of 100mPa. And (4) soaking the MOFs organic gas separation membrane prepared in the step (6) into a silane coating liquid, standing for 100s, and taking out, wherein the thickness of the coating liquid is 5-10 micrometers.
(8) Thermal crosslinking: and carrying out thermal crosslinking on the coated organic gas separation membrane at 80 ℃ for 1h to finally obtain the organic gas separation membrane with a three-layer structure.
The performance test data of the membrane shows that the flux of nitrogen under 0.1Mpa can reach 1.086 multiplied by 10-7mol/(m2s.Pa) and a flux of 0.03298X 10 of propylene gas-7mol/(m2s.Pa), and a nitrogen/propylene separation coefficient of 32.92.
Comparative example 1
(1) Preparation of precursor solution
Dissolving 0.42g of zirconium chloride and 0.30g of terephthalic acid in 67.5mLN, N-Dimethylformamide (DMF), adding 32 mu L of deionized water, fully dissolving the reagents by stirring and ultrasonic treatment, and transferring the clear precursor solution to a hydrothermal kettle;
(2) thermal treatment
And (3) vertically soaking a hollow fiber membrane of polyvinylidene fluoride (PVDF) in the prepared precursor solution by using a fixed frame, and carrying out heat treatment for 72h at the constant temperature of 120 ℃. During the heat treatment, the hollow fiber membranes are all dissolved in the precursor solution, and the preparation of the separation membrane cannot be further completed.
The conditions of the base film and the solution after the reaction are shown in FIG. 6.
Comparative example 2
(1) Precursor solution required for preparing MOFs film
The same as in example 1.
(2) Pretreatment of base film
(a) The same as example 1;
(b) a polyvinylidene fluoride (PVDF) membrane having a pore diameter of 500nm was used as in example 1. Heat treatment is carried out for 72h under the constant temperature condition of 120 ℃. During the heat treatment, the hollow fiber membrane is dissolved in the precursor solution, and the preparation of the separation membrane cannot be further completed.
The conditions of the base film and the solution after the reaction are shown in FIG. 7.
Comparative example 3
(1) Preparation of precursor solution
Dissolving 0.42g of zirconium chloride and 0.30g of terephthalic acid in 67.5mLN, N-Dimethylformamide (DMF), adding 32 mu L of deionized water, fully dissolving the reagents by stirring and ultrasonic treatment, and transferring the clear precursor solution to a hydrothermal kettle;
(2) thermal treatment
Vertically soaking a polypropylene hollow fiber base membrane with the aperture of 500nm in the prepared precursor solution by using a fixing frame, carrying out heat treatment for 72 hours at the constant temperature of 120 ℃, and naturally cooling after the heat treatment is finished;
(3) ultrasonic treatment
Taking out the molten film, carrying out ultrasonic treatment for 5s, and removing particles with poor binding force to obtain a substrate with seed crystals; (4) forming a continuous film
The substrate on which the seed crystal was deposited was heat-treated twice in the same manner as in (2) to obtain a continuous film, and the film was washed with DMF and then with methanol and dried at room temperature.
The surface electron microscope of the prepared film is shown in fig. 8, and as can be seen from fig. 8, the octahedral structures in the MOFs functional layer of the prepared film exist independently, and do not form a structure embedded with each other.
Comparative example 4
(1) Solution required for preparing MOFs membrane
Mixing N-methyl pyrrolidone, terephthalic acid, zirconium tetrachloride and pure water according to the molar ratio of 400:1:1:0.01, and fully stirring to obtain a solution required by MOFs membrane preparation.
(2) Polymerizing with a pore diameter of 500nmPropylene hollow fiber base membrane, the ratio of the surface area of the base membrane to the solution in (1) is 1m2and/L (namely, a membrane with the surface of 1 square meter is placed into 1L of MOFs preparation solution in the step (1A)), immersing the membrane into the MOFs preparation solution to prepare a first mixture, introducing nitrogen for protection, and carrying out in-situ growth reaction for 24 hours at 120 ℃ to prepare the separation membrane.
(3) And (3) taking out the separation membrane prepared in the step (2), and cleaning unreacted monomers and solvents on the surface of the membrane to obtain the MOFs organic gas separation membrane.
(4) And (4) cleaning the separation membrane in the step (3) to obtain the MOFs organic gas separation membrane.
The surface of the prepared film was subjected to an electron microscope as shown in fig. 9, and as can be seen from fig. 9, when the base film was not pretreated, some discontinuous crystals were attached to the base film, and the crystals were formed by grouping a plurality of octahedrons together, and a continuous structure was not formed.
Any limitations of the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (18)
1. A metal-organic framework material separation membrane comprises a base membrane and a metal-organic framework material functional layer, wherein the metal-organic framework material functional layer comprises a plurality of polyhedron structures embedded with each other;
preferably, the polyhedron is constructed by a plurality of crystal lattices, and the mutual lattice shared by two adjacent polyhedrons in the mutually embedded polyhedron structure and/or the distance between the centers of the two adjacent polyhedrons is smaller than the average value L of the lengths of the two adjacent polyhedrons, preferably smaller than 0.95L, and more preferably 0.2-0.9L;
preferably, at least 20% of the polyhedrons of said functional layer of metal-organic framework material are intercalated, preferably at least 30%, preferably at least 40%, preferably at least 50%, preferably at least 60%, preferably at least 80% of the polyhedrons are intercalated;
preferably, the polyhedron comprises hexahedrons and/or octahedrons, preferably the polyhedron has a length of 50-2000 nm;
preferably, the crystal lattice is composed of metal atoms and organic ligands; preferably, the metal atom is selected from a zirconium atom, a niobium atom, a molybdenum atom or a cobalt atom; preferably the organic ligand is selected from terephthalic acid and/or nitroterephthalic acid.
2. The separation membrane according to claim 1, wherein the hexahedron has a length of 50 to 1000nm, and wherein the hexahedron having a length of 400 to 600nm accounts for 50 to 80%.
3. The separation membrane according to claim 1, wherein the length of the octahedron is 200-2000nm, and the proportion of the octahedron having a length of 800-1200nm is 60-80%.
4. Separation membrane according to any one of claims 1 to 3, wherein the functional layer of metal-organic framework metal material has an average pore size of 0.1 to 2.0nm, preferably 0.30 to 0.96 nm; and/or the presence of a gas in the gas,
the thickness of the metal-organic framework material functional layer is 200-5000nm, preferably 1000-5000 nm.
5. The separation membrane of any one of claims 1 to 4, wherein the base membrane is selected from one or more of a polypropylene membrane, a polyethylene membrane, a polyvinyl chloride membrane, or a polytetrafluoroethylene membrane; and/or the presence of a gas in the gas,
the pore diameter of the basement membrane is 10-10000nm, preferably 50-5000nm, and more preferably 200-1000 nm.
6. The separation membrane according to any one of claims 1 to 5, further comprising a silicone layer on a surface of the metal-organic framework material functional layer.
7. A preparation method of a metal-organic framework material separation membrane comprises the following steps:
(1) preparing a solution comprising a first organic solvent, an organic ligand, a first metal compound and an adjuvant selected from water or glacial acetic acid;
(2) pretreating the base film, and introducing metal atoms in the first metal compound in the step (1) into the surface of the base film;
(3) mixing the base membrane pretreated in the step (2) with the solution in the step (1) to obtain a first mixture, and heating the first mixture to react to obtain the metal-organic framework material separation membrane;
(4) optionally, the separation membrane is subjected to a cleaning treatment.
8. The method according to claim 7, wherein in the step (1), the molar ratio of the first organic solvent, the organic ligand and the first metal compound is (10-1000): 1-100, preferably (100-1000): 1-10, more preferably (100-700):1:1, further preferably (400-600):1:1, and/or the molar ratio of the first organic solvent and the auxiliary agent water is 100 (0.001-0.005), and the molar ratio of the first organic solvent and the auxiliary agent glacial acetic acid is 100 (20-60);
preferably, the first organic solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide and dimethylacetamide,
preferably, the organic ligand is selected from terephthalic acid and/or nitroterephthalic acid;
preferably, the first metal compound is selected from one or more of a zirconium compound, a niobium compound, a molybdenum compound and a cobalt compound, preferably zirconium tetrachloride.
9. The method of claim 7 or 8, wherein the base film is selected from one or more of a polypropylene film, a polyethylene film, a polyvinyl chloride film, or a polytetrafluoroethylene film;
and/or the pore size of the base membrane is 10-10000nm, preferably 50-5000nm, more preferably 200-1000 nm.
10. The method according to any one of claims 7-9, wherein the step (2) comprises the steps of:
(2A-1) preparing a solution comprising polyacrylic acid, polyvinyl alcohol, and a second metal compound,
(2A-2) coating the solution of the step (2A-1) on a base film;
preferably, the polyacrylic acid comprises polyacrylic acid and partially hydrolyzed polyacrylic acid, and/or the mass concentration of the polyacrylic acid and the polyvinyl alcohol in the solution is 500-2000mg/L, and the molar ratio of the total of the polyacrylic acid and the polyvinyl alcohol to the metal compound is 1-3: 1;
preferably, the metal atom in the second metal compound is the same as the metal atom in the first metal compound in step (1), preferably the second metal compound is selected from one or more of a zirconium compound, a niobium compound, a molybdenum compound and a cobalt compound, preferably zirconium tetrachloride;
preferably, in the step (2A-2), the ratio of the surface area of the base film to the volume of the solution obtained in the step (2A-1) is 0.1 to 10m2/L, preferably 0.5 to 5m2a/L, more preferably 1 to 2m2/L。
11. The method according to any one of claims 7-9, wherein the step (2) comprises the steps of:
(2B-1) preparing a solution comprising the metal complex represented by the formula I and a second organic solvent,
(2B-2) mixing the base film with the solution of the step (2B-1),
(2B-3) cleaning the mixed base film in the step (2B-2) by adopting a third solvent;
in the formula I, Q is selected from amido, carbonyl or alkylene of C1-C6; r1Selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy or halogen; m1The same metal atom as that in the first metal compound in the step (1), preferably M1Selected from zirconium atoms, niobium atoms, molybdenum atoms or cobalt atoms; m is 5 to 20; n is 1 to 10;
preferably, the second organic solvent is selected from one or more organic solvents capable of swelling the base membrane, preferably from one or more aliphatic hydrocarbons of C5-C10, halogenated aliphatic hydrocarbons of C1-C10, aromatic hydrocarbons of C6-C20 and halogenated aromatic hydrocarbons of C6-C20, more preferably from one or more of n-pentane, n-hexane, trichloromethane, carbon tetrachloride, benzene and toluene; the third solvent is selected from one or more of solvents capable of deswelling the swollen base film, preferably from water;
preferably, in the solution of the step (2B-1), the mass concentration of the metal complex shown in the formula I is 500-2000 mg/L;
preferably, in the step (2B-2), the ratio of the surface area of the base film to the volume of the solution obtained in the step (2B-1) is 0.1 to 10m2/L, preferably 0.5 to 5m2a/L, more preferably 1 to 2m2/L。
12. The method according to any one of claims 7-9, wherein the step (2) comprises the steps of:
(2C-1) preparing a solution containing the metal complex represented by the formula II,
(2C-2) mixing the base film with the solution of the step (2C-1) to obtain a mixture, and polymerizing the mixture under the microwave radiation condition;
in the formula II, X is selected from amido, carbonyl or alkylene of C1-C6; r2、R3And R4The same or different, each is independently selected from hydrogen, alkyl of C1-C6,Alkoxy of C1-C6 or halogen; m2The same metal atom as that in the first metal compound in the step (1), preferably M2Selected from zirconium atoms, niobium atoms, molybdenum atoms or cobalt atoms;
preferably, the solution of the metal complex in the step (2C-1) is an aqueous solution of the metal complex, and/or the mass concentration of the metal complex represented by the formula II is 500 to 20000 mg/L;
preferably, in the step (2C-2), the ratio of the surface area of the base film to the volume of the solution obtained in the step (2C-1) is 0.1 to 10m2/L, preferably 0.5 to 5m2a/L, more preferably 1 to 2m2/L；
Preferably, in the step (2C-2), the microwave radiation has a microwave intensity of 500 to 2000. mu.w/cm2The frequency is 1000-200000 Hz.
13. The method according to any one of claims 7 to 12, wherein in step (3), the ratio of the surface area of the base film pretreated in step (2) to the volume of the solution obtained in step (1) is (0.01 to 100) m2/L。
14. The method according to any of claims 7-13, characterized in that the method further comprises the steps of:
(5) performing one or more times of repairing treatment on the metal-organic framework material separation membrane obtained in the step (3) or (4);
preferably, the repair process comprises the steps of:
(A) mixing a metal-organic framework material separation membrane with a solution containing a first organic solvent, an organic ligand, a first metal compound and an auxiliary agent to obtain a second mixture, wherein the auxiliary agent is selected from water or glacial acetic acid;
(B) heating the second mixture to react to prepare a metal-organic framework material separation membrane;
(C) optionally, the separation membrane is subjected to a cleaning treatment.
15. The process according to any one of claims 7 to 14, wherein the reaction temperature in step (3) is 50 to 300 ℃, the reaction pressure is 0.01 to 0.5MPa, and the reaction time is 1 to 100 hours, preferably 10 to 72 hours, more preferably 15 to 30 hours; and/or the presence of a gas in the gas,
the reaction temperature in the step (B) is 50-300 ℃, the reaction pressure is 0.01-0.5MPa, and the reaction time is 1-100h, preferably 5-50h, and more preferably 10-20 h.
16. The method according to any of claims 7-15, characterized in that the method further comprises the steps of: coating silane coating liquid on the surface of the metal-organic framework material separation membrane prepared in the step (3) or (4) or (B) or (C), heating the metal-organic framework material separation membrane coated with the silane coating liquid, and enabling the silane coating liquid to perform a crosslinking reaction to obtain the metal-organic framework material separation membrane comprising the organic silicon layer;
preferably, the temperature of the crosslinking reaction is 50-300 ℃ and the time is 0.1-20 h.
17. A metal-organic framework material separation membrane prepared according to the method of any one of claims 7-16.
18. Use of a metal-organic framework material separation membrane according to any of claims 1-6 or a metal-organic framework material separation membrane prepared according to the method of any of claims 7-16 for organic matter separation.
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| 秦茜 等: "表面修饰在MOF薄膜制备中的应用", 《化工进展》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115739064A (en) * | 2022-11-22 | 2023-03-07 | 杭州中科沐森环保科技有限公司 | Nano material for ultraviolet light catalytic degradation and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2023546896A (en) | 2023-11-08 |
| CN116474573A (en) | 2023-07-25 |
| US20230415101A1 (en) | 2023-12-28 |
| EP4230284A1 (en) | 2023-08-23 |
| CN114425243B (en) | 2023-05-12 |
| WO2022077562A1 (en) | 2022-04-21 |
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